JP2015091948A - Cured product of curable polyorganosiloxane composition, adhesive body using the curable polyorganosiloxane composition, manufacturing method of adhesive body using the curable polyorganosiloxane composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable product capable of being obtained by using a curable polyorganosiloxane composition excellent in quick curability, excellent in transparency.SOLUTION: There is provided a cured product of a curable polyorganosiloxane composition containing (A) alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in a molecule, (B) polyorganohydrogensiloxane having two or more hydrogen atoms binding to a silicon atom in a molecule and (C) a platinum catalyst, where a ratio of the number of hydrogen atoms binding to the silicon atom of (B) Hto the number of the alkenyl group of (A) Viis from 0.5 to 100, (C) is from 0.5 to 1000 ppm as a platinum-based metal atom, and a composition before curing contains two or more parts selected from the group consisting of a part containing (B), a part containing (B) and (A), a part containing (C) and a part containing (C) and (A).

Description

  The present invention relates to a cured product of a curable polyorganosiloxane composition, an adhesive body using the curable polyorganosiloxane composition, and a method for producing an adhesive body using the curable polyorganosiloxane composition.

  In a display device such as a mobile phone provided with a display component such as a liquid crystal module, a glass or resin screen is installed on the front surface of the display device for the purpose of protecting the display device or improving design. However, since an air layer exists between the screen and the display device, there is a problem that it is difficult to see the display screen due to reflection of external light. Therefore, the air layer is bonded with a transparent adhesive that matches the refractive index of the screen. As an adhesive used therefor, an ultraviolet curable type is generally used. The adhesive is applied to one side of opposing members to be bonded, and the members are bonded together, and then cured with ultraviolet rays.

  In recent years, the use of plastic resin that is difficult to transmit ultraviolet rays to the screen material due to the variety of designs and the provision of frame printing with colored areas around the screen has increased the number of cases where ultraviolet rays do not transmit and are difficult to cure. It is coming. On the other hand, Patent Document 1 discloses that a compound having an average of at least one hydrolyzable silyl group in one molecule and an average of at least one polymerizable carbon-carbon double bond in one molecule. A curable composition containing the compound is disclosed. The composition described in Patent Document 1 is a curable composition that can be quickly cured by light and that is cured by reacting with moisture in the atmosphere even in a portion that is not exposed to light. Patent Document 2 discloses a two-component addition reaction type silicone gel that is cured by heating.

JP 2010-248347 A JP 2004-272059 A

  In the composition disclosed in Patent Document 1, since curing occurs in the coating apparatus, the problem of causing clogging of the coating apparatus and a long reaction time with moisture in the first place, the curing reaction after bonding is very slow. There was a problem.

  When the thermosetting composition disclosed in Patent Document 2 is interposed between the display device and the protective plate and thermally cured, there is a problem that the curing time is long and the protective plate is displaced. Although it is conceivable to cure the protective plate in a short time by applying a high temperature, there is a problem that sufficient heat cannot be applied for curing because of the heat resistance of the member to be bonded. .

  As described above, it is not necessary to use a special device such as radiation or a heating device in the curing reaction, and even a member that does not transmit ultraviolet rays or a member having poor heat resistance can be bonded, and it is not affected by the external environment such as moisture. It is suitable for the bonding method in which the curing reaction starts when the adhesive components are applied to the base material to be bonded to each other, the base materials are bonded to each other, and the adhesive components are in contact with each other. There is a growing demand for new curable polyorganosiloxane compositions that give cured products with excellent transparency.

  An object of this invention is to provide the hardened | cured material which is obtained using the curable polyorganosiloxane composition excellent in quick-curing property, and has the outstanding transparency.

The following is mentioned as this invention and its suitable aspect.
[1] (A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1000 ppm as a platinum-based metal atom,
A cured product of a curable polyorganosiloxane composition,
The composition before curing is
A portion containing (B),
A portion comprising (B) and (A);
Including two or more parts selected from the group consisting of a part containing (C) and a part containing (C) and (A),
Cured product of curable polyorganosiloxane composition.
[2] A layer in which the composition before curing contains (B),
A layer comprising (B) and (A);
A layered product including a layer containing (C) and two or more layers selected from the group consisting of a layer containing (C) and (A).
Hardened | cured material of curable polyorganosiloxane composition of [1].
[3] A layer in which the composition before curing contains (B),
A layer comprising (B) and (A);
The cured product of [1] or [2], which is a laminate comprising three or more layers selected from the group consisting of a layer containing (C) and a layer containing (C) and (A).
[4] Any of [1] to [3], wherein the composition before curing is a laminate in which layers containing (B) and (A) and layers containing (C) are alternately laminated Some cured products.
[5] The cured product according to any one of [1] to [4], wherein the composition before curing is a laminate having a layer containing (C) at both ends.
[6] The cured product according to any one of [1] to [4], wherein the composition before curing is a laminate having layers containing (B) and (A) at both ends.
[7] A substrate with a cured product, having the cured product of any one of [1] to [6] on one substrate.
[8] An adhesive body comprising two substrates, wherein the two substrates are bonded via the cured product of any one of [1] to [6].
[9] (A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1000 ppm as a platinum-based metal atom,
A method for producing an adhesive body comprising two substrates using a curable polyorganosiloxane composition,
Step 1A: From the part containing (B), the part containing (B) and (A), the part containing (C), and the part containing (C) and (A) on the adherend surface of one substrate A step of forming two or more parts selected from the group to form a curable polyorganosiloxane composition before curing; and step 2A: laminating the other substrate to form a curable polyorganosiloxane composition. The manufacturing method of the adhesive body containing the two base materials including the process of bonding together base materials.
[10] Step 1A includes Step 1A-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C ) And (A), the production method of [9], which is a step of laminating two or more layers selected from the group consisting of layers comprising a curable polyorganosiloxane composition.
[11] Step 1A is Step 1A-2: Three layers including a layer containing (C), a layer containing (B) and (A), and a layer containing (C) on the adherend surface of one substrate. Are manufactured in this order to form a laminate of the curable polyorganosiloxane composition. [9]
[12] Step 1A includes Step 1A-3: a layer containing (B) and (A), a layer containing (C), and (B) and (A) on the adherend surface of one substrate. The method according to [9], wherein the three layers are laminated in this order to form a laminate of the curable polyorganosiloxane composition.
[13] (A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1000 ppm as a platinum-based metal atom,
A method for producing an adhesive body comprising two substrates using a curable polyorganosiloxane composition,
Step 1B: From the part containing (B), the part containing (B) and (A), the part containing (C), and the part containing (C) and (A) on the adherend surface of one substrate Forming two or more parts selected from the group consisting of:
Step 2B: a part containing (B), a part containing (B) and (A), a part containing (C), and a part containing (C) and (A) on the adherend surface of the other substrate A step of forming one or more portions selected from the group consisting of: and step 3B: obtained in step 1B and step 2B via two or more portions obtained in step 1B and one or more portions obtained in step 2B. Including the step of bonding substrates together, the composition of the portion obtained by combining the portion obtained in step 1B and the portion obtained in step 2B is a composition of a curable polyorganosiloxane composition, and includes two substrates Manufacturing method of adhesive body.
[14] Step 1B is Step 1B-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C ) And (A) to form a laminate by forming two or more layers selected from the group consisting of layers.
Step 2B includes Step 2B-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and (A) is a step of forming a laminate by forming one or more layers selected from the group consisting of layers comprising:
[13] The production method.
[15] Step 1B is Step 1B-2: a layer containing (C) is laminated on the adherend surface of one of the substrates, and then a layer containing (B) and (A) is laminated. The process of obtaining
Step 2B is Step 2B-2: a step of obtaining a laminate by laminating a layer containing (C) on the adherend surface of the other substrate.
[13] The production method of [14].
[16] Step 1B is Step 1B-3: a layer containing (B) and (A) is laminated on the adherend surface of one of the substrates, and then a layer containing (C) is laminated. The process of obtaining
Step 2B is Step 2B-3: a step of obtaining a laminate by laminating a layer containing (B) and (A) on the adherend surface of the other substrate.
[13] The production method of [14].
[17] One substrate is a base having an image display unit of the image display device, the other substrate is a light-transmitting protective unit of the image display device, and the adhesive is an image display device. A manufacturing method according to any one of [9] to [16].

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material which is obtained using the curable polyorganosiloxane composition excellent in quick-curing property and has the outstanding transparency is provided.

<Curable polyorganosiloxane composition>
Each component contained in the curable polyorganosiloxane composition (hereinafter also simply referred to as “composition”) will be described.

(A) The alkenyl group-containing polyorganosiloxane is a component that becomes a base polymer in the composition. By blending (A), it is possible to ensure a stable three-dimensional structure due to a crosslinking reaction during curing, to control curing shrinkage, and to ensure good visibility. (A) has an average of two or more alkenyl groups bonded to a silicon atom in one molecule, and can form a network structure by addition reaction with the Si—H bond of (B). There is no particular limitation. Typically, the general formula (I):
(R ^a ) _n1 (R ^b ) _n2 SiO _{(4-n1-n2) / 2} (I)
(Where
R ^a is a C ₂ -C ₆ alkenyl group (eg, vinyl, allyl, 3-butenyl, 5-hexenyl);
R ^b is a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl) or phenyl;
n1 is 1 or 2;
n2 is an integer of 0 to 2, provided that n1 + n2 is 1 to 3)
Is an alkenyl group-containing polyorganosiloxane having an average of at least two alkenyl group-containing siloxane units in the molecule. The number of alkenyl groups bonded to the silicon atom in (A) is preferably from 2 to 100 on average per molecule, and more preferably from 2 to 50.

  The siloxane skeleton of (A) may be linear or branched. Since the synthesis and control of the average degree of polymerization are easy, (A) is preferably a straight chain. Moreover, you may use these mixtures.

R ^a is preferably a vinyl group because it is easy to synthesize and does not impair the fluidity before curing and the heat resistance of the cured product. R ^a may be present at either the end or in the middle of the polyorganosiloxane molecular chain of (A), or may be present at both of them, in order to give excellent mechanical properties to the composition after curing. Is preferably present at least at both ends thereof.

^Rb is particularly preferably a methyl group from the viewpoints of easy synthesis and excellent balance between fluidity and mechanical strength after curing.

  n1 is preferably 1 because synthesis is easy.

  From the viewpoint of workability, (A) preferably has a viscosity at 23 ° C. of 1 to 100,000 cP, more preferably 1 to 50,000 cP, and particularly preferably 1 to 15,000 cP. preferable. It is preferable to adjust the weight average molecular weight of (A) so as to be in these viscosity ranges. Moreover, it is more preferable to use together (A) with a high viscosity and (A) with a low viscosity so that it may become these viscosity ranges. In this specification, the viscosity is a value measured at 23 ° C. using a rotational viscometer.

（式中、
Ｒ^ａは、独立して、Ｃ_２−Ｃ_６アルケニル基（例えば、ビニル、アリル、３−ブテニル、５−ヘキセニル、好ましくはビニル）であり、
Ｒ^ｂは、独立して、Ｃ_１−Ｃ_６アルキル基（例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、好ましくはメチル）又はフェニル基であり、
ｍ１は、（Ａ）の２３℃における粘度を１〜１００，０００ｃＰ（好ましくは１〜５０，０００ｃＰ、より好ましくは１〜１５，０００ｃＰ）にする数である）で示されるアルケニル基含有直鎖状ポリオルガノシロキサンが好ましい。 Therefore, as (A), the formula (Ia):

(Where
R ^a is independently a C ₂ -C ₆ alkenyl group (eg, vinyl, allyl, 3-butenyl, 5-hexenyl, preferably vinyl);
R ^b is independently a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group;
m1 is an alkenyl group-containing linear chain represented by (A) having a viscosity of 1 to 100,000 cP (preferably 1 to 50,000 cP, more preferably 1 to 15,000 cP) at 23 ° C. Polyorganosiloxane is preferred.

  Further, (A) is a polymethylvinylsiloxane having both ends blocked with dimethylvinylsiloxane units and an intermediate unit consisting of dimethylsiloxane units, and having a viscosity at 23 ° C. of 1 to 100,000 cP (preferably 5 to 5). An alkenyl group-containing linear polyorganosiloxane having a molecular weight of 50,000 cP, more preferably 10 to 15,000 cP is more preferable.

(B) The polyorganohydrogensiloxane functions as a crosslinking agent in (A) by the addition of ^a hydrosilyl group contained in the molecule with Ra in (A). In order to reticulate the cured product, there is no particular limitation as long as it has an average of two or more hydrogen atoms bonded to silicon atoms involved in the addition reaction. Such polyorganohydrogensiloxane is typically represented by the general formula (II):
(R ^c ) _n3 (R ^d ) _n4 SiO _{(4-n3-n4) / 2} (II)
(Where
R ^c is a hydrogen atom,
R ^d is a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group;
n3 is 1 or 2;
n4 is an integer of 0 to 2, provided that n3 + n4 is 1 to 3)
2 or more units in the molecule.

R ^d is exemplified by those similar to R ^b in (A) described above, including preferred ones. Further, n3 is preferably 1 because synthesis is easy.

  The siloxane skeleton in (B) may be linear, branched or cyclic, and is preferably linear or cyclic. Moreover, you may use these mixtures.

  (B) preferably has a viscosity at 23 ° C. of 1 to 10,000 cP, more preferably 1 to 1,000 cP, still more preferably 1 to 200 cP, and more preferably 1 to 50 cP. Particularly preferred.

When (B) is cyclic, (B1) R ^e ₂ HSiO _1/2 unit (wherein R ^e is a hydrogen atom or a C ₁ -C ₆ alkyl group (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl) , preferably of a is) and SiO _4/2 units methyl), in one molecule, a hydrogen atom bonded to a silicon atom having at least two, cyclic polyorganohydrogensiloxane.

(B1) is a cyclic polyorganohydrogensiloxane composed of R ^e ₂ HSiO _1/2 units and SiO _4/2 units and having two or more hydrogen atoms bonded to silicon atoms in one molecule. The number of hydrogen atoms in (B1) is preferably 3 to 100 and more preferably 3 to 50 in one molecule. R ^e as the C ₁ -C ₆ alkyl group is preferably methyl from the viewpoint of easiness of synthesis and the like.

As (B1), the ratio of R ^e ₂ HSiO _1/2 unit and SiO _4/2 unit is 1.5 to 2.2 mol of R ^e ₂ HSiO _1/2 unit with respect to 1 mol of SiO _4/2 unit. Is preferable, and 1.8 to 2.1 mol is more preferable. Typically, 3-5 SiO, such as [R ^e ₂ HSiO _1/2 ] ₈ [SiO _4/2 ] ₄ or [R ^e ₂ HSiO _1/2 ] ₁₀ [SiO _4/2 ] _{5 4/2} units form a cyclic siloxane skeleton, which each _{SiO 4/2} unit two ^R _e 2 _{HSiO 1/2} units combined is preferably, particularly preferably, the _{SiO 4/2} units Are bonded with _two (CH ₃ ) ₂ HSiO _1/2 units.

  The viscosity of (B1) is preferably 1 to 100 cP, and more preferably 1 to 50 cP.

When (B) is linear, both ends are independently blocked with R ₃ SiO _1/2 units, and the intermediate unit is composed of R ₂ SiO _2/2 units (wherein R is hydrogen An atom, a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group, provided that at least two of R are hydrogen It is a linear polyorganohydrogensiloxane having a viscosity at 23 ° C. of 1 to 10,000 cP (preferably 1 to 5,000 cP, more preferably 1 to 1,000 cP). The hydrogen atom bonded to the silicon atom may be present at the terminal or in the intermediate unit.

（式中、
Ｒ^ｃは、水素原子であり、
Ｒ^ｄは、独立して、Ｃ_１−Ｃ_６アルキル基（例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、好ましくはメチル）又はフェニル基であり、
ｍ２は、（Ｂ２）の２３℃における粘度を１〜１０，０００ｃＰ（好ましくは１〜５，０００ｃＰ、より好ましくは１〜１，０００ｃＰ）とする数である）で示される、直鎖状ポリオルガノハイドロジェンシロキサン；
（Ｂ３）両末端がＲ^ｄ _３ＳｉＯ_１／２単位で閉塞され、中間単位がＲ^ｃＲ^ｄＳｉＯ_２／２単位及びＲ^ｄ _２ＳｉＯ_２／２単位（式中、Ｒ^ｃは、水素原子であり、Ｒ^ｄは、独立して、Ｃ_１−Ｃ_６アルキル基（例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、好ましくはメチル）又はフェニル基である）からなり、２３℃における粘度が１〜１０，０００ｃＰ（好ましくは１〜５，０００ｃＰ、より好ましくは１〜１，０００ｃＰ）である、直鎖状ポリオルガノハイドロジェンシロキサン；及び
（Ｂ４）両末端がＲ^ｃＲ^ｄ _２ＳｉＯ_１／２単位で閉塞され、中間単位がＲ^ｃＲ^ｄＳｉＯ_２／２単位及びＲ^ｄ _２ＳｉＯ_２／２単位（式中、Ｒ^ｃは、水素原子であり、Ｒ^ｄは、独立して、Ｃ_１−Ｃ_６アルキル基（例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、好ましくはメチル）又はフェニル基である）からなり、２３℃における粘度が１〜１０，０００ｃＰ（好ましくは１〜５，０００ｃＰ、より好ましくは１〜１，０００ｃＰ）とする数である）である、直鎖状ポリオルガノハイドロジェンシロキサンが挙げられる。 For example, (B2) Formula (III):

(Where
R ^c is a hydrogen atom,
R ^d is independently a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group;
m2 is a linear polyorgano represented by (B2) having a viscosity of 1 to 10,000 cP (preferably 1 to 5,000 cP, more preferably 1 to 1,000 cP) at 23 ° C. Hydrogen siloxane;
(B3) Both ends are blocked with R ^d ₃ SiO _1/2 units, intermediate units are R ^c R ^d SiO _2/2 units and R ^d ₂ SiO _2/2 units (wherein R ^c is a hydrogen atom) R ^d independently consists of a C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group, and has a viscosity at 23 ° C. A linear polyorganohydrogensiloxane that is 1 to 10,000 cP (preferably 1 to 5,000 cP, more preferably 1 to 1,000 cP); and (B4) both ends are R ^c R ^d ₂ SiO _{1 / 2} units are blocked and the intermediate units are R ^c R ^d SiO _2/2 units and R ^d ₂ SiO _2/2 units (wherein R ^c is a hydrogen atom and R ^d is independently C ₁ -C ₆ alkyl group For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group) and a viscosity at 23 ° C. of 1 to 10,000 cP (preferably 1 to 5,000 cP, more preferably 1). A linear polyorganohydrogensiloxane, which is a number of ˜1,000 cP).

  (B2) is a linear polyorganohydrogensiloxane represented by the formula (III).

R ^d in (B2) is preferably a methyl group from the viewpoints of easy synthesis and excellent balance of properties such as mechanical strength and fluidity before curing.

  (B2) is preferably polymethylhydrogensiloxane in which both ends are blocked with dimethylhydrogensiloxane units and the intermediate unit is composed of dimethylsiloxane units.

  The viscosity of (B2) is 1 to 10,000 cP, more preferably 1 to 5,000 cP, and still more preferably 1 to 1,000 cP.

(B3) is a polyorganohydrogensiloxane in which both ends are blocked with R ^d ₃ SiO _1/2 units, the intermediate unit is R ^c R ^d SiO _2/2 units, and R ^d ₂ SiO _2/2 units. It is. R ^c in (B3) is preferably 2 to 5,000, more preferably 3 to 5,000, and still more preferably 20 to 1,000 in one molecule. R ^d in (B3) is preferably a methyl group from the viewpoint of easy synthesis and excellent balance of properties such as mechanical strength and fluidity before curing.

As (B3), the ratio of R ^c R ^d SiO _2/2 units to R ^d ₂ SiO _2/2 units is R ^c R ^d SiO _{2/2 with} respect to 1 mol of R ^d ₂ SiO _2/2 units. What a unit is 0.1-2.0 mol is preferable, and what is 0.5-1.5 mol is more preferable. Therefore, as (B3), both ends are blocked with trimethylsiloxane units, the intermediate unit is composed of a dimethylsiloxane unit and a methylhydrogensiloxane unit, and 0.1 mol of methylhydrogensiloxane unit per 1 mol of dimethylsiloxane unit. Polymethylhydrogensiloxane that is ˜2.0 mol is preferred.

  The viscosity of (B3) is 1 to 10,000 cP, more preferably 1 to 5,000 cP, and still more preferably 1 to 1,000 cP.

(B4) is a polyorganohydrogensiloxane in which both ends are blocked with R ^c R ^d ₂ SiO _1/2 units and the intermediate units are R ^c R ^d SiO _2/2 units and R ^d ₂ SiO _2/2 units. It is. R ^c in (B4) is preferably 2 to 5,000 in one molecule, more preferably 3 to 5,000, and still more preferably 3 to 1,000. R ^d in (B4) is preferably a methyl group from the viewpoint of easy synthesis and excellent balance of properties such as mechanical strength and fluidity before curing.

The ^(B4), the ratio of R ^c R _{d SiO 2/2} units and ^R _d 2 _{SiO 2/2} ^units, with respect to _R d _{2 SiO 2/2} units to 1 ^mol, R ^c R _{d SiO 2/2} What a unit is 0.1-2.0 mol is preferable, and 0.5-1.5 mol is more preferable. Therefore, as (B4), both ends are blocked with dimethylhydrogensiloxane units, the intermediate unit is composed of dimethylsiloxane units and methylhydrogensiloxane units, and the number of methylhydrogensiloxane units is 0 with respect to 1 mol of dimethylsiloxane units. A polymethylhydrogensiloxane that is .1 to 2.0 moles is preferred.

  The viscosity of (B4) is 1 to 10,000 cP, more preferably 1 to 5,000 cP, and still more preferably 1 to 1,000 cP.

(B) may be a branched polyorganohydrogensiloxane, for example, R ₂ HSiO _1/2 unit (wherein R is a hydrogen atom, a C ₁ -C ₆ alkyl group (eg, methyl, ethyl , Propyl, butyl, pentyl, hexyl, preferably methyl) or a phenyl group) and a SiO _4/2 unit, and a polyalkylhydrogensiloxane having 3 or more hydrogen atoms bonded to a silicon atom in one molecule Is mentioned. R ₃ SiO _1/2 unit, R ₂ SiO unit and RSiO _3/2 unit (wherein R is a hydrogen atom, a C ₁ -C ₆ alkyl group (for example, methyl, ethyl, propyl, butyl, pentyl, Hexyl, preferably methyl) or a phenyl group), and a polyalkylhydrogensiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule. The viscosity at 23 ° C. of the branched polyorganohydrogensiloxane is 1 to 10,000 cP, more preferably 1 to 5,000 cP, and still more preferably 1 to 1,000 cP.

(B) may be used alone or in combination of two or more. (B1), (B2), (B3) and (B4) can be used alone or in combination. From the viewpoint of increasing curability, it is preferable to use (B1). As (B), the combined use of (B1) and (B2), the combined use of (B1) and (B4), the combined use of (B3) and (B2) are preferable, and the combined use of (B1) and (B2) is more preferable. As (B), when (B1) and (B2) are used in combination, the amount of hydrogen in (B1) relative to the total amount of hydrogen in (B1) and (B2) (H _B1 / (H _B1 + H _B2 )) is preferably 0.05 to 0.60, and more preferably 0.10 to 0.50.

From the viewpoint of ensuring proper cure rate, the ratio of the total number Vi _A of alkenyl groups bonded to silicon atoms, the total number H _B of the hydrogen atoms bonded to silicon atoms in (B) of (A) ( H _B / Vi _a) is a 0.5 to 100, preferably from 0.5 to 50.0. When (H _B / Vi _A ) is less than 0.5, a crosslinking agent sufficient for curing cannot be diffused, so that it does not cure, and when it exceeds 100, there are few crosslinking points and it does not cure.

  (C) contained in the composition is a catalyst for promoting the addition reaction between the alkenyl group of (A) and the Si—H group of (B). From the viewpoint of good catalytic activity, platinum-based metal (platinum group element) compounds such as platinum, rhodium and palladium are preferably used. Chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, platinum-olefin complexes Platinum compounds such as platinum-vinylsiloxane complexes, platinum-ketone complexes, platinum compounds such as platinum-phosphine complexes, rhodium-phosphine complexes, rhodium compounds such as rhodium-sulfide complexes, and palladium compounds such as palladium-phosphine complexes. A compound is more preferable, and a platinum-vinylsiloxane complex is more preferable.

  (C) is 0.5 to 1, in terms of platinum metal atoms, with respect to the total weight of (A) to (C), from the viewpoint of ensuring the transparency of the cured product and ensuring an appropriate curing rate. 000 ppm, preferably 0.5 to 500 ppm, more preferably 0.5 to 200 ppm. Curing is slow when the amount of (C) is less than 0.5 ppm. When the amount of (C) is more than 1,000 ppm, in addition to the significant decrease in transparency, discoloration of the cured product becomes significant and the cured product becomes black. In addition, (C) may be more than 5 ppm and 1,000 ppm or less, or more than 200 ppm and 1,000 ppm or less in terms of platinum-based metal atoms, based on the total weight of (A) to (C). It may be 0.5 ppm or more and less than 5 ppm and more than 200 ppm and 1,000 ppm or less.

  The composition can contain (D) a stabilizer having a nitrogen atom, (E) a diluent, (F) an adhesion-imparting agent, (G) an inorganic filler, and the like as long as the effects of the present invention are not impaired. . In addition, it is preferable that a composition does not contain (D) component.

The composition may contain (D) a stabilizer having a nitrogen atom. (D) can stabilize (C) the platinum-based catalyst. (D) is, for example, a general formula: (R ¹ ) ₂ N—R ³ —N (R ² ) ₂ (wherein R ¹ independently represents a C ₁ -C ₆ alkyl group (for example, Methyl, ethyl, propyl, butyl, pentyl, hexyl), R ² has the same meaning as R ¹ , or is a hydrogen atom, and R ³ is a C ₂ -C ₄ alkylene group (eg, ethylene, And an amine compound represented by the following formula:

  As (D), specifically, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, N, N, N ′, N′-tetramethylethylenediamine is preferred. (D) can be used alone or in combination of two or more.

  The blending amount of (D) is preferably in the range of 0.001 to 0.5 mol, more preferably 0.01 to 0.1 mol, with respect to 1 mol of the platinum-based metal atom of (C). Within such a range, the appearance of the resulting catalyst can be prevented from poor appearance over time, discoloration can be suppressed, and curing in a desired time can be achieved without extremely reducing the catalytic activity of (C). .

  The composition may contain (E) a diluent. When the composition contains (E), the viscosity is adjusted. (E) is a silicone oil that does not contain an alkenyl group involved in the curing reaction, and is preferably a polymethylsiloxane in which both ends are blocked with trimethylsiloxane units and an intermediate unit is composed of dimethylsiloxane units. (E) preferably has a viscosity at 23 ° C. of 1 to 5,000 cP, and more preferably 5 to 1,000 cP. The blending amount of (E) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight in total of (A) to (C) in the composition, 20 weights. More preferably, it is less than or equal to parts.

  The composition may contain (F) an adhesion-imparting agent. (F) Di, tri, tetra, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane Alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane 3-glycidoxypropyl group-containing alkoxysilanes; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4- Epoxy cyclohe 2- (3,4-epoxycyclohexyl) ethyl group-containing alkoxysilanes such as syl) ethyl (methyl) dimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxy Alkenylalkoxysilanes such as silane, allyltrimethoxysilane, allyltriethoxysilane, methylallyldimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl (methyl) (Meth) actyl such as dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl (methyl) dimethoxysilane B propyl alkoxysilanes; 1,1,3,5,7- organosilicon compounds such as reaction products of pentamethyl cyclotetrasiloxane and 3-methacryloxypropyl trimethoxy silane.

（式中、Ｑ^１及びＱ^２は、互いに独立して、アルキレン基、好ましくはＣ_１−Ｃ_４アルキレン基を表し、Ｒ^３は、Ｃ_１−Ｃ_４アルキル基を表す）で示される側鎖を有する有機ケイ素化合物が挙げられる。 As an organosilicon compound, for example, specifically, the following formula:

(Wherein Q ¹ and Q ² independently of each other represent an alkylene group, preferably a C ₁ -C ₄ alkylene group, and R ³ represents a C ₁ -C ₄ alkyl group). An organosilicon compound having

As such an organosilicon compound, the following compounds are preferable.

  The composition may contain (G) an inorganic filler. Examples of the inorganic filler (G) include dry fine powder silica such as fumed silica and arc silica, and fumed silica is preferable. In addition, such a silica surface is treated with a silazane compound such as hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane; a polyorganosiloxane such as octamethylcyclotetrasiloxane. Etc. may be processed.

<Hardened product of curable polyorganosiloxane composition>
A cured product of the curable polyorganosiloxane composition (hereinafter also simply referred to as “cured product”) is a curable polyorganosiloxane composition before curing (hereinafter also simply referred to as “composition before curing”). , A part containing (B), a part containing (B) and (A), a part containing (C), and a part containing (C) and (A) (hereinafter referred to as “four curable parts”) Including two or more curable portions selected from the group consisting of:
Here, the part containing (C) and the part containing (C) and (A) correspond to the curing agent component in the curable polyorganosiloxane composition. The part containing (C) and the part containing (C) and (A) are also collectively referred to as “first component”. The part containing (B) and the part containing (B) and (A) correspond to the main ingredient component in the curable polyorganosiloxane composition. The part containing (B) and the part containing (B) and (A) are also collectively referred to as “second component”.

  The part containing (B), the part containing (B) and (A), the part containing (C), and the part containing (C) and (A) are curable parts contained in the composition before curing. . The curable part is not cured alone, but (B) and (C) contained in each part come into contact only at the time of curing, and the crosslinking reaction proceeds. In the present invention, the curable portion can be distinguished by the presence of each component. For example, the part containing (B) and (A) and the part containing (B) can be distinguished by the presence of (A). Moreover, the part containing (B) and (A) and the part containing (C) and (A) can be distinguished by the presence of (B) and (C).

  In the composition before curing, at least one part containing (B) or part containing (B) and (A) is at least one part containing (C) or part containing (C) and (A). It touches. In the composition before curing, the second component and the first component are stored separately, and are different from the two-component curable composition used as an adhesive after being mixed before being applied to the substrate. .

  The number and type of the curable portions are not particularly limited as long as the composition including the curable portions contained in the composition before curing is the composition of the curable polyorganosiloxane composition described above. For example, when the composition before curing consists of two curable parts, the composition before curing consists of a part containing (B) and a part containing (C) and (A), or (B) and It consists of a part containing (A) and a part containing (C), or consists of a part containing (B) and (A) and a part containing (C) and (A).

  It is preferable that the composition before hardening contains three or more curable portions selected from the group consisting of four curable portions. Moreover, it is more preferable that the composition before hardening consists of three curable parts: a part containing (C), a part containing (B) and (A), and a part containing (C).

  When the composition before curing includes a plurality of parts containing (C) and (A), in order to allow the crosslinking reaction to proceed uniformly, (A) contained in the part containing each (C) and (A) is Preferably they are the same. For the same reason, when the composition before curing includes a plurality of parts containing (B) and (A), it is preferable that (A) contained in the parts containing (B) and (A) is the same. .

  The curable portion can include (D) to (F) described above. The part containing (C) and the part containing (C) and (A) are (E) from the viewpoint of fast curing and from the viewpoint of reducing discoloration (particularly yellowing) of the resulting cured product. Is more preferable, and (E) and (D) are more preferable. Moreover, it is preferable that the part containing (B) and the part containing (B) and (A) further contain (F) from an adhesive viewpoint.

  The shape of each part of the curable part is not particularly limited, and may be linear, columnar, circular, spherical and layered. These can be appropriately selected according to the viscosity of the coating apparatus and the composition.

  The curable portion is preferably layered. That is, the composition before curing is a layer containing (B), a layer containing (B) and (A), a layer containing (C), and a layer containing (C) and (A) (hereinafter referred to as these). A laminate including two or more layers selected from the group consisting of “four curable layers”) is preferable. Further, in the present invention, the composition before curing preferably includes three curable layers: a layer containing (C), a layer containing (B) and (A), and a layer containing (C). preferable.

  The layer containing (B), the layer containing (B) and (A), the layer containing (C), and the layer containing (C) and (A) are curable layers contained in the composition before curing. . The composition before curing is more preferably a laminate in which layers containing (B) and (A) and layers containing (C) are alternately laminated. When (A) and (B) coexist and (A) and (C) do not coexist, (C) easily moves to the portion containing the component (B), and the curing reaction easily proceeds. Moreover, the composition before curing is more preferably a layered body having a layer containing (C) at both ends or a layered body containing (B) and (A), and a layered layer having a layer containing (C) at both ends. The body is particularly preferred. When the composition before curing is a laminate having a layer containing (C) at both ends, more (C) moves from both ends to the portion containing the component (B) existing inside the laminate. The curing reaction of the composition is more likely to proceed from both ends.

  Although the total thickness of a laminated body is not specifically limited, It is preferable that it is 2-2,000 micrometers, It is more preferable that it is 2-1,000 micrometers, It is especially preferable that it is 10-500 micrometers.

  Moreover, it is preferable that the thickness of each layer in a laminated body is as follows according to the kind of curable layer. The thickness of the layer containing (B) is preferably 10 to 1000 μm, and more preferably 20 to 500 μm. The thickness of the layer containing (B) and (A) is preferably 1 to 500 μm, and more preferably 10 to 300 μm. The thickness of the layer containing (C) is preferably 0.1 to 1000 μm, and more preferably 0.1 to 300 μm. The thickness of the layer containing (C) and (A) is preferably from 0.1 to 50 μm, and more preferably from 0.5 to 30 μm. In addition, when a laminated body contains two or more same curable layers, said thickness is the thickness of each curable layer.

When a plurality of parts containing (C) and (A) and parts containing (B) and (A) are included, as long as the H _B / Vi _A ratio specified for the composition is satisfied, (C) and (A ) And the content ratio of (A) contained in the part containing (B) and (A) are not particularly limited. The amount of (A) in the part containing (C) and (A) is 0.1 to 300 parts by weight relative to 100 parts by weight of (A) in the part containing (B) and (A). Preferably, it is 0.1 to 200 parts by weight.

  The content of the first component and the second component in the composition before curing is preferably such that the total of the second component is 200 to 100,000 parts by weight with respect to the total of 100 parts by weight of the first component, The amount is more preferably 200 to 50,000 parts by weight, still more preferably 200 to 10,000 parts by weight, and particularly preferably 200 to 5,000 parts by weight. From the viewpoint of the speed of the temporary fixing time, the total amount of the second component is preferably 200 to 10,000 parts by weight, and more preferably 200 to 5,000 parts by weight.

  In the composition before curing, the first component preferably has a viscosity at 23 ° C. of 1 to 100,000 cP, more preferably 1 to 10,000 cP, and 1 to 5,000 cP. More preferably, it is 1 to 1,000 cP, particularly preferably 1 to 500 cP. If it is such a range, the workability | operativity at the time of forming the composition before hardening will improve, each component contained in a 1st component and a 2nd component will be easy to mix, reactivity will improve, and hardening time further Shortened. In addition, in the addition reaction between (A) and (B), (C) is likely to penetrate into the region of (B), (B) and (A), thereby further shortening the curing time. Therefore, it is preferable that a polyorganosiloxane having a small molecular chain, that is, a low viscosity (A) is present. From the viewpoint of obtaining such a first component, it is preferable that the first component contains a polyorganosiloxane having a low viscosity as (A) (for example, a viscosity at 23 ° C. of 1 to 500 cP). From the viewpoint of obtaining the first component having the above-mentioned viscosity, it is preferable that the first component further contains (E) or the first component further contains (F). Alternatively, the first component is a portion containing (C) and further contains (E) or (F), or the first component is a portion containing (A) and (C), The polyorganosiloxane having a viscosity at 23 ° C. of 1 to 500 cP is preferably included.

  The second component preferably has a viscosity at 23 ° C. of 1 to 100,000 cP, more preferably 100 to 100,000 cP, still more preferably 500 to 50,000 cP, and 1,000 to It is particularly preferably 50,000 cP, more preferably 3,000 to 20,000 cP. In such a range, workability is improved, spreadability at the time of application is good, each component contained in the first component and the second component is easily mixed at the time of bonding, the reactivity is improved, and curing is performed. Time is further reduced. In addition, in the addition reaction between (A) and (B), a large cross-linked structure is formed at a small number of reaction points, which further shortens the curing time. High (A) is preferably included. From the viewpoint of obtaining such a second component, polyorganosiloxane having a high viscosity (for example, a viscosity at 23 ° C. of 30,000 to 100,000 cP) and a low viscosity (for example, a viscosity at 23 ° C.) as (A). Preferably contain a mixture of 50 to 1,000 cP) polyorganosiloxane. In the mixture of the polyorganosiloxane having a high viscosity and the polyorganosiloxane having a low viscosity, the amount of the polyorganosiloxane having a low viscosity is not particularly limited as long as the above viscosity is satisfied. For example, 100 parts by weight of the polyorganosiloxane having a high viscosity The amount can be 0.1 to 100 parts by weight.

  In a mixture of a polyorganosiloxane having a viscosity of 1000 to 100,000 cP at 23 ° C. and a polyorganosiloxane having a viscosity of 50 to 500 cP at 23 ° C., the amount of the polyorganosiloxane having a viscosity of 50 to 500 cP is The viscosity is not particularly limited as long as the above viscosity is satisfied. For example, the viscosity can be 0.1 to 1,000 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having a viscosity of 1,000 to 100,000 cP. . Similarly, in a mixture of a polyorganosiloxane having a viscosity of 5,000 to 100,000 cP and a polyorganosiloxane having a viscosity of 50 to 1,000 cP at 23 ° C., a polyorgano having a viscosity of 50 to 1,000 cP. The amount of siloxane can be 0.1 to 1,000 parts by weight with respect to 100 parts by weight of polyorganosiloxane having a viscosity of 5,000 to 100,000 cP.

  A cured product of the composition is obtained by contacting the first component and the second component. The cured product of the composition has excellent transparency. An example of the transparency index is that the transmittance of the cured product of the composition is 50% or more. The transmittance of the cured product of the composition is preferably 80 to 100%, and more preferably 90 to 100%. The transmittance is a value measured at 400 nm and a sample thickness of 180 μm. Generally, in the cured product of the curable polyorganosiloxane composition, the transmittance of the cured product of the composition in the visible light wavelength region (mainly 400 to 800 nm) has a minimum transmittance at 400 nm. In general, when yellowing, cloudiness, or the like occurs in the cured product of the curable polyorganosiloxane composition, the transmittance with respect to light having a shorter wavelength decreases. Therefore, when the transmittance at 400 nm of the cured product of the composition is 50% or more, the transmittance of the visible light wavelength region of the cured product of the composition is 50% or more, and the cured product of the composition is excellent in transparency. It has sex. Therefore, when the composition is used to bond the base portion having the image display portion of the image display device and the translucent protective portion, the visibility is good. The yellow index, which is the degree of discoloration of the cured product of the composition, is not particularly limited, but is preferably 0.01 to 15, and more preferably 0.01 to 5.0. When the yellow index is 15 or less, it can be said that the cured product of the composition has little discoloration. Therefore, when a yellow index is 15 or less and a base material having an image display part of an image display device and a translucent protective part are bonded using a composition that gives a cured product having excellent transparency, Visibility is further improved.

  It is preferable that the composition before hardening is more obtained by the process 1A, the process 1B, and the process 2B in the manufacturing method of the adhesive body mentioned later.

(Substrate with cured product and adhesive)
The present invention also relates to a substrate with a cured product, in which a cured product of the composition is laminated on one substrate. The present invention also relates to an adhesive body including two base materials in which the two base materials are bonded via a cured product of the composition.

  In the composition before curing, each curable part may be formed in a direction perpendicular to the surface of the substrate to which the curable part is applied (longitudinal direction), and the curable part is applied to the curable part. Each curable portion may be formed in a direction parallel to the surface of the substrate to be formed (lateral direction). Even if the curable portion is formed in the direction parallel to the substrate, the curing reaction proceeds by contacting (B) and (C) contained in the composition before curing. In the case where the curable portion is a laminate, the layer may be laminated in a direction perpendicular to the surface of the substrate to which the curable layer is applied (longitudinal direction). It means that layers may be laminated in a direction parallel to the surface of the material (lateral direction). Even if the curable layer is laminated in parallel with the surface of the substrate to which the curable layer is applied, the curing reaction proceeds by contacting (B) and (C) contained in the composition before curing. To do.

  In the cured product, when the composition before curing is a laminate laminated in a direction perpendicular to the surface of the substrate to which the curable portion is applied, the layer of the cured product in contact with the substrate is cured as described above. It corresponds to one of both ends of the previous laminate. Therefore, the base material with a cured product of the present invention is a laminate in which the composition before curing is a layer containing (B) and (A) at one end or a layer containing (C). It is more preferable that the both ends are layers containing (B) and (A) or a layer containing (C), more preferably a layered body where both ends are layers containing (C). Is particularly preferred.

  Base materials include metals such as aluminum, iron, zinc, copper, magnesium alloys, epoxy resins, acrylic resins, plastics such as ABS, PA, PBT, PC, PPS, SPS, and glass, cathode ray tubes, liquid crystals, plasma The base of the image display unit of the image display device such as organic EL and the light-transmitting protective unit are preferable.

  Although the thickness of the hardened | cured material in a base material with hardened | cured material and the thickness of the hardened | cured material of the composition in the adhesive body containing two base materials are not specifically limited, It is preferable that it is 2-2,000 micrometers, 2-1 Is more preferably 1,000 μm, particularly preferably 10 to 500 μm.

In the substrate with a cured product, the cured product of the composition is bonded to the substrate. Moreover, the hardened | cured material of the composition in a base material with hardened | cured material is used preferably as a dam material. For example, the dam material is used as a frame for preventing the sealant from flowing out when the image display unit is sealed.
The adhesive is preferably used as described later.

  The substrate with a cured product is preferably obtained by a method for producing a substrate with a cured product, which will be described later. Moreover, it is preferable that an adhesive body is obtained by the manufacturing method of the adhesive body mentioned later.

<Method for Producing Adhesive Body Containing Two Substrates Using Curable Polyorganosiloxane Composition>
In the method for producing an adhesive body comprising two substrates using a curable polyorganosiloxane composition, the curable polyorganosiloxane composition of the present invention is applied to one substrate, and the other substrate is used. 1st manufacturing method including bonding, and 2nd manufacturing including applying both some base materials by applying a part of curable polyorganosiloxane composition of this invention to both base materials Including methods.

(First manufacturing method)
The first manufacturing method includes the steps 1A to 2A.
Step 1A includes a part containing (B), a part containing (B) and (A), a part containing (C), and a part containing (C) and (A) on the adherend surface of one substrate. Forming a curable polyorganosiloxane composition before curing by forming two or more parts selected from the group consisting of:

  In the step 2A, the shape of the two or more portions is not particularly limited as long as (B) and (C) of the curable portion come into contact with each other, the curing reaction proceeds, and an adhesive body is obtained. As described in the composition before curing. Moreover, the formation area of each part in a base material will not be specifically limited if (B) and (C) in a curable part contact in process 2A, hardening reaction advances, and an adhesive body is obtained. It may be formed on a part of the base material or on the entire adhesive surface of the base material.

  In step 1A, the means for forming each part is not particularly limited, but it can be formed by applying a curable part. The application method is not particularly limited as long as it can be accurately applied to the position of the surface to be bonded and the composition can be formed on the entire bonded body, and examples thereof include a method using a dispenser and a slot die coater.

  The application to the substrate can be performed by applying the curable portion to a part or the entire surface of the adhesive surface of the substrate. For example, a 1st component can be formed with respect to the one part area | region of a base material, and a 2nd component can also be formed with respect to the area | region where the 1st component of the same base material is not formed.

  In Step 1A, the amount of each part formed is as described for the first component and the second component in the composition before curing, including preferable ones.

  In Step 1A, the first component preferably has a viscosity at 23 ° C. of 1 to 100,000 cP, more preferably 1 to 10,000 cP, and still more preferably 1 to 1,000 cP. It is particularly preferably 1 to 500 cP. The second component preferably has a viscosity at 23 ° C. of 1 to 100,000 cP, more preferably 100 to 100,000 cP, still more preferably 1,000 to 50,000 cP, It is particularly preferably 3,000 to 20,000 cP. With such viscosities of the first component and the second component, the workability is improved, the spreadability at the time of application is good, and the components contained in the first component and the second component are mixed at the time of bonding. The reactivity is easily improved and the curing time is further shortened.

  The total content of the first component and the total content of the second component is, from the point of speed of temporary fixing time, 1: 1,000 to 1, 000: 1, preferably 1: 500 to 500: 1, more preferably 1: 200 to 200: 1, still more preferably 1: 2 to 1: 100, A ratio of 1: 2 to 1:50 is particularly preferred.

  As Step 1A, Step 1A-1: A layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and ( A step of laminating two or more layers selected from the group consisting of A) and forming a laminate of the curable polyorganosiloxane composition is preferred. Also, as step 1A, step 1A-2: three layers including a layer containing (C), a layer containing (B) and (A), and a layer containing (C) on the adherend surface of one substrate. Lamination in this order to form a laminate of a curable polyorganosiloxane composition, and 1A-3: a layer containing (B) and (A) on the adherend surface of one substrate, (C ) And a layer containing (B) and (A) are laminated in this order to form a laminate of the curable polyorganosiloxane composition. As step 1A, 1A-2 is particularly preferable.

The coating thickness of the first component and the second component is not particularly limited, but is preferably 1 to 1,000 μm, and more preferably 1 to 500 μm from the viewpoint of the speed of temporary fixing time. From the viewpoint of workability, the coating thickness of the first component is preferably 1 to 50 μm, and more preferably 2 to 30 μm. Similarly, the coating thickness of the second component is preferably 10 to 300 μm, and more preferably 20 to 200 μm.
In addition, when forming two or more 1st components and 2nd components, said application | coating thickness is a layer thickness of each part. For example, in Step 1A-2, when three layers including a layer containing (C), a layer containing (B) and (A), and a layer containing (C) are formed in this order, two (C) The coating thickness of the containing layer is preferably 1 to 50 μm, more preferably 2 to 30 μm, and more preferably 2 to 30 μm, and the coating thickness of the layer containing (B) and (A) is 1 to 500 μm. Is preferable, and it is more preferable that it is 10-300 micrometers.

  The ratio between the coating thickness of the first component and the coating thickness of the second component is not particularly limited, but is preferably 1: 1,000 to 1,000: 1, and 1: 500 to 500: 1. Is more preferably 1: 200 to 200: 1, particularly preferably 1: 2 to 1: 100, and particularly preferably 1: 2 to 1:50.

  From the viewpoint of transparency, the total coating thickness of the first component and the second component is preferably 2 to 2000 μm, more preferably 2 to 1000 μm, and particularly preferably 10 to 500 μm.

  The part containing (C) and the part containing (C) and (A) are uniformly kneaded by mixing means such as a universal kneader or a kneader with (C) and other components blended as necessary. Can be prepared. In addition, the part containing (B) and the part containing (B) and (A) should be prepared in the same manner as the first component using (B) and other components blended as necessary. Can do.

  Step 2A is a step of laminating the other substrate and bonding the substrates together via the curable polyorganosiloxane composition. By the step 2A, an bonded body manufactured by the first manufacturing method is obtained.

  Although the method of bonding base materials is not specifically limited, The method of bonding under vacuum and the method of bonding under atmospheric pressure are mentioned. In the present invention, (C) present in the first component and (B) present in the second component come into contact with each other and are cured in 1 second to 30 minutes, thereby exhibiting adhesive force. . The curing time is preferably 1 second to 20 minutes, more preferably 1 second to 15 minutes. Therefore, although process 2A needs to be performed within 1 second-30 minutes from process 1A, process 1A and process 2A can be performed by a continuous process.

(Second manufacturing method)
The second manufacturing method of the present invention includes steps 1B to 3B.
Step 1B includes a part containing (B), a part containing (B) and (A), a part containing (C), and a part containing (C) and (A) on the adherend surface of one substrate. Forming two or more portions selected from the group consisting of:
The composition of the curable polyorganosiloxane composition of the present invention is that the two or more parts obtained in step 1B are composed of two or more parts obtained in step 1B and one or more parts obtained in step 2B. If it is, it will not be specifically limited. Further, the composition of two or more parts obtained in step 1B may be the composition of the curable polyorganosiloxane composition of the present invention.

  In Step 1B, the portion to be formed is as described in Step 1A, including preferable ones. In step 1B, each part is preferably formed of a layer. Therefore, Step 1B is Step 1B-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and The step of forming a laminate by forming two or more layers selected from the group consisting of layers containing (A) is preferred.

Step 2B includes a part including (B), a part including (B) and (A), a part including (C), and (C) and (A) on the surface to be bonded of the other substrate. It is a step of forming one or more parts selected from the group consisting of parts.
In Step 2B, the portion to be formed is as described in Step 1A, including preferable ones.
In step 2B, each part is preferably formed of a layer. Therefore, the step 2B is the step 2B-1: on the adherend surface of the other substrate, the layer containing (B), the layer containing (B) and (A), the layer containing (C), and (C) And a step of forming a laminate by forming one or more layers selected from the group consisting of layers containing (A).

  In the second production method, since the one in which (C) and (B) are in contact with each other at the time of bonding is preferable in terms of rapid curing, the portion formed on the adhesive surface of one substrate in step 1B, and the step In 2B, the pair formed with the portion formed on the adhesive surface of the other substrate includes the pair including (C) and the portion including (B) and (A), and (C) and (A). It is preferably a set of a part and a part containing (B), and a part containing (C) and (A) and a part containing (B) and (A). That is, it is preferable that the group formed last in step 1B and the group formed last in step 2B are the aforementioned groups.

  Furthermore, in the second manufacturing method, since a desired bonded body can be obtained with few steps, Step 1B and Step 2B are Step 1B-2 and Step 2B-2, and Step 1B-3 and Step 2B-3. Is preferred. Here, step 1B-2 is a step of laminating a layer containing (C) on the adherend surface of one base material and then laminating layers containing (B) and (A) to obtain a laminate. It is. Step 2B-2 is a step of obtaining a laminate by laminating a layer containing (C) on the adherend surface of the other substrate. Step 1B-3 is a step in which a layer containing (B) and (A) is laminated on the adherend surface of one substrate, and then a layer containing (C) is laminated to obtain a laminate. Step 2B-3 is a step of obtaining a laminate by laminating layers containing (B) and (A) on the adherend surface of the other substrate.

  For example, in Step 2B-2, when a layer containing (C) is laminated and then a layer containing (B) and (A) is laminated, the coating thickness of the layer containing (C) is 0.1 to 50 μm. It is preferable that it is 0.1 to 30 μm, and the coating thickness of the layer containing (B) and (A) is preferably 1 to 500 μm, more preferably 10 to 300 μm. . Step 2B-2: When the layer containing (C) is laminated on the adherend surface of the other substrate, the coating thickness of the layer containing (C) is preferably 0.1 to 50 μm. 0.1 to 30 μm is more preferable.

Step 3B is a step of bonding the substrates obtained in Step 1B and Step 2B together via two or more portions obtained in Step 1B and one or more portions obtained in Step 2B. By the step 3B, the bonded body manufactured by the second manufacturing method of the present invention is obtained.
The step of bonding the base materials in step 3B is as described in step 2A, including preferable ones.

  In the 1st and 2nd manufacturing method, the process of heating at the temperature of 50-80 degreeC may be included depending on the case after the process of bonding and hardening and adhere | attaching base materials. Thereby, hardening is accelerated | stimulated more and adhesive force becomes higher. Although heating time can be set suitably, it can be set as 0.1 minute-3 hours, for example.

  The first and second manufacturing methods are useful for a method for manufacturing an image display device. That is, in the first and second manufacturing methods, one base material is a base portion having an image display portion of the image display device, and the other base material is a translucent protective portion of the image display device. The adhesive is preferably an image display device. In the preferred manufacturing method described above, the base of the image display unit may be provided with a step for preventing the composition from flowing out at the outer peripheral edge as necessary.

  Specifically, as the image display device obtained by the manufacturing method of the present invention, the image display device is a large (50 to 100 inches) plasma panel display or the like, or the image display device is a small (less than 1 to 50 inches) portable. For example, telephone. Further, these image display devices may include a touch sensor.

<Method for producing substrate with cured product using curable polyorganosiloxane composition>
The present invention also relates to a method for producing a substrate with a cured product. The manufacturing method of the base material with hardened | cured material of this invention is the process 1C: On a base material, the part containing (B), the part containing (B) and (A), the part containing (C), and (C) And forming two or more parts selected from the group consisting of the parts containing (A) to form a curable polyorganosiloxane composition before curing.
A base material with a cured product is obtained by curing the curable polyorganosiloxane composition before curing obtained in Step 1C. The conditions in step 1C are as described in step 1A.

  In the first and second production methods, an adhesive can be produced using the curable polyorganosiloxane composition as part of the adherend surface. In addition, a curable polyorganosiloxane composition is used for a part of the adherend surface, and the remaining part is an adhesive having a composition different from that of the composition (for example, a one-component polyorganosiloxane composition having low reactivity). An adhesive body may be manufactured using an adhesive). From the viewpoint of uniformity of properties such as optical properties and adhesiveness of the obtained cured product, the composition is different from (A) and (B) contained in the curable polyorganosiloxane composition of the present invention. The alkenyl group-containing polyorganosiloxane and polyorganohydrogensiloxane contained in the adhesive are the same as the former (A) and the latter alkenyl group-containing polyorganosiloxane, and the former (B) and the latter polyorganohydrosiloxane. It is preferred that the disiloxanes are the same.

  In addition, this invention relates also to the composition used for the above-mentioned manufacturing method. Specifically, the composition of the present invention is an adhesive for bonding two substrates, and can be used as an adhesive for bonding two substrates including the steps 1A to 2A. . Here, Step 1A and Step 2A are as described above including preferable ones. Moreover, the composition of this invention is an adhesive agent for bonding two base materials, Comprising: It can be used as an adhesive agent for bonding two base materials containing the said process 1B-3B. Here, Steps 1B to 3B are as described above including preferable ones. Thus, the composition of the present invention can be used as an adhesive for bonding various substrates. The composition of the present invention is preferably an adhesive for bonding a base portion of an image display portion of an image display device such as a cathode ray tube, liquid crystal, plasma, organic EL or the like and a translucent protective portion.

  In the composition, (C) present in the first component and (B) present in the second component are contacted and then cured at room temperature (for example, 20 to 25 ° C.) to exhibit adhesive strength. That is, the composition can be cured only by storing the first component and the second component as they are in different containers and contacting them at the time of use. In addition, since a composition contains (A), as a set of a 1st component and a 2nd component, a 1st component is a part containing (C), and a 2nd component is a part containing (B). Except time.

Next, an Example and a comparative example are given and this invention is demonstrated further in detail. However, the present invention is not limited to these examples. The composition which consists of the 1st component of an Example and a comparative example, and a 2nd component was prepared by mixing each component with the composition shown in Table 1-Table 3.
Each component used is as follows.
A1: Polymethylvinylsiloxane having both ends blocked with dimethylvinylsiloxane units and intermediate units consisting of dimethylsiloxane units (viscosity at 23 ° C., 82,000 cP)
A2: Polymethylvinylsiloxane in which both ends are blocked with dimethylvinylsiloxane units and the intermediate units are dimethylsiloxane units (viscosity at 23 ° C .: 420 cP)
A3: Polymethylvinylsiloxane in which both ends are blocked with dimethylvinylsiloxane units and the intermediate units are dimethylsiloxane units (viscosity at 23 ° C. is 15 cP)
B1: The average unit formula is [H (CH ₃ ) ₂ SiO _1/2 ] ₈ [SiO _4/2 ] ₄ (hydrogen amount: 1.05% by weight)
B2: Polymethylhydrogensiloxane having both ends blocked with dimethylhydrogensiloxane units and intermediate units consisting of dimethylsiloxane units (viscosity at 23 ° C. of 20 cP)
C: a complex obtained by heating chloroplatinic acid to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at a molar ratio of 1: 4 and having a platinum content of 4.91% by weight .
E1: Polymethylsiloxane (viscosity at 23 ° C. of 100 cP) in which both ends are blocked with trimethylsiloxane units and intermediate units are dimethylsiloxane units
F1: 3-methacryloxypropyltrimethoxysilane

<Examples 1-14, Comparative Examples 1-4>
The physical properties were evaluated as follows.
(1) Viscosity The viscosity at 23 ° C. was measured using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.).

(2) Temporary fixing time (Examples 1 to 12, Comparative Examples 1 to 4)
As a substrate, two parallel plates (thickness 1 mm, diameter 25 mm, made of aluminum) were used. The first component was applied to the entire surface of the first substrate in an amount that would result in a first component application thickness, and the first component was applied to the entire surface of the second substrate in an amount that would result in a first component application thickness. Subsequently, the 2nd component was apply | coated by the quantity used as the 2nd component application thickness on the 2nd base material which apply | coated the 1st component. Immediately after applying the second component onto the second substrate, the total thickness of the first component and the second component is 180 μm through the first component and the second component via the first component and the second component. It bonded so that it might become, and the bonded body of the 1st base material and the 2nd base material was obtained. Immediately after obtaining the bonded body, measurement of the temporary fixing time was started.
The temporary fixing time was measured at 25 ° C. using a viscoelasticity measuring apparatus (ARES manufactured by TA Instruments Japan Co., Ltd.) at a frequency of 10 Hz and a strain of 2%. The time when the storage elastic modulus reached 150 Pa was defined as a temporary fixing time.
(Examples 13 to 14)
As a substrate, two parallel plates (thickness 1 mm, diameter 25 mm, made of aluminum) were used. The first component was applied to the entire surface of the first base material in an amount to achieve the first component application thickness, and the second component was applied to the entire surface of the second base material in an amount to provide the second component application thickness. The first base material and the second base material are bonded to each other through the first component and the second component so that the total thickness of the first component and the second component is 180 μm. A bonded body of materials was obtained. Immediately after obtaining the bonded body, measurement of the temporary fixing time was started. The measurement of the temporary fixing time is the same as described above.

(3) Yellow index (Examples 1 to 12, Comparative Examples 1 to 4)
Two glass plates (5 cm × 5 cm × 1 mm thickness) were used as the substrate. The 1st component was apply | coated to the whole surface of a 1st base material, and the whole surface of a 2nd base material in the quantity used as 1st component application | coating thickness. Subsequently, the 2nd component was apply | coated by the quantity used as 2nd component application | coating thickness on the 1st base material which apply | coated the 1st component. Immediately after the second component is applied on the first substrate, the total thickness of the first component and the second component is measured at 25 ° C. by a spacer in which the first substrate and the second substrate are previously arranged on the substrate. Was bonded via the first component and the second component to obtain a bonded body of the first base material and the second base material. The bonded body is obtained by heat-treating the bonded body at 25 ° C. for 30 minutes and at 70 ° C. for 30 minutes, and the first base material and the second base material are bonded via the cured products of the first component and the second component. Got. After returning the bonded body to a state of 25 ° C., a yellow index, which is an index of the degree of discoloration, was measured. The yellow index was measured using a spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.).
(Examples 13 to 14)
Two glass plates (5 cm × 5 cm × 1 mm thickness) were used as the substrate. The first component was applied to the entire surface of the first substrate in an amount that would provide the first component application thickness, and the second component was applied to the entire surface of the second substrate in an amount that would provide the second component application thickness. At 25 ° C., the first base material is bonded to the first base material with a spacer previously arranged on the base material so that the total thickness of the first component and the second component is 180 μm. And the bonded body of the 2nd substrate was obtained. The bonded body is obtained by heat-treating the bonded body at 25 ° C. for 30 minutes and at 70 ° C. for 30 minutes, and the first base material and the second base material are bonded via the cured products of the first component and the second component. Got. After returning the bonded body to a state of 25 ° C., the yellow index was measured. The yellow index measurement is the same as described above.

(4) Transmittance For Examples 1 to 14 and Comparative Examples 1 to 4, adhesive bodies were prepared by the same method as the above “(3) Yellow Index”. About the adhesive body, the transmittance | permeability in wavelength 400nm which is a parameter | index of a transparency degree was measured using the spectrophotometer (CM-3500d by Minolta Co., Ltd.).

The results are summarized in a table. In the measurement of the yellow index and the transmittance, the thickness of the cured product of the first component and the second component, that is, the thickness of the cured product of the curable polyorganosiloxane composition was 180 μm.

*Ｖｉ_Ａは、Ａ１〜Ａ３（実施例１〜実施例１４及び比較例１〜比較例３）、又は、Ａ１（比較例４）に含まれるケイ素原子に結合したビニル基の合計
*Ｈ_Ｂは、Ｂ１及びＢ２に含まれるケイ素原子に結合した水素原子の合計
*Ｈ_Ｂ１は、Ｂ１に含まれるケイ素原子に結合した水素原子の合計
*Ｈ_Ｂ２は、Ｂ２に含まれるケイ素原子に結合した水素原子の合計
＊仮固定時間における「３０分以上」は、３０分経過した後であっても貯蔵弾性率が１５０Ｐａに到達しないことを示す

* Vi _A is the sum of vinyl groups bonded to silicon atoms contained in A1 to A3 (Examples 1 to 14 and Comparative Examples 1 to 3) or A1 (Comparative Example 4).
* H _B is the sum of hydrogen atoms bonded to silicon atoms contained in B1 and B2.
* H _B1 is the total number of hydrogen atoms bonded to silicon atoms contained in B1
* H _B2 is the total number of hydrogen atoms bonded to silicon atoms contained in B2 * "30 minutes or more" in the temporary fixing time indicates that the storage elastic modulus does not reach 150 Pa even after 30 minutes have elapsed.

  In Examples, when the first component and the second component were brought into contact with each other, both showed excellent rapid curability. From these, according to the present invention, it is not necessary to use a special device such as a radiation or a heating device in the curing reaction, and even a member that does not transmit ultraviolet rays or a member having poor heat resistance can be bonded, and the external environment such as moisture can be bonded. It can be seen that a curing reaction is possible without being affected, and an adhesive body including two substrates can be manufactured. On the other hand, in the comparative example, the curable polyorganosiloxane composition does not satisfy the provisions of the present invention. The cured product of Comparative Example 2 had a low transmittance and was inferior in transparency. In addition, the cured product of Comparative Example 2 had a high yellow index and significant discoloration. Moreover, 30 minutes or more passed until Comparative Examples 1, 3, and 4 exhibited curability and adhesiveness.

  The cured product of the curable polyorganosiloxane composition of the present invention and the method for producing an adhesive using the curable polyorganosiloxane composition are used for bonding various substrates, particularly images of cathode ray tubes, liquid crystals, plasma, organic EL, etc. This is useful in bonding a base portion having an image display portion of a display device and a translucent protective portion.

Claims (17)

(A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1,000 ppm as a platinum-based metal atom,
A cured product of a curable polyorganosiloxane composition,
The composition before curing is
A portion containing (B),
A portion comprising (B) and (A);
Including two or more parts selected from the group consisting of a part containing (C) and a part containing (C) and (A),
Cured product of curable polyorganosiloxane composition. A layer in which the composition before curing contains (B);
A layer comprising (B) and (A);
A layered product including a layer containing (C) and two or more layers selected from the group consisting of a layer containing (C) and (A).
A cured product of the curable polyorganosiloxane composition according to claim 1. A layer containing the composition (B) before curing,
A layer comprising (B) and (A);
The hardened | cured material of Claim 1 or 2 which is a laminated body containing 3 or more layers selected from the group which consists of a layer containing (C) and a layer containing (C) and (A).   The composition according to any one of claims 1 to 3, wherein the composition before curing is a laminate in which layers containing (B) and (A) and layers containing (C) are alternately laminated. object.   The hardened | cured material of any one of Claims 1-4 whose composition before hardening is a laminated body which has a layer containing (C) in both ends.   The hardened | cured material of any one of Claims 1-4 whose composition before hardening is a laminated body which has a layer containing (B) and (A) in both ends.   The base material with hardened | cured material which has the hardened | cured material of any one of Claims 1-6 on one base material.   The adhesive body containing two base materials with which the two base materials were adhere | attached through the hardened | cured material of any one of Claims 1-6. (A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1000 ppm as a platinum-based metal atom,
A method for producing an adhesive body comprising two substrates using a curable polyorganosiloxane composition,
Step 1A: From the part containing (B), the part containing (B) and (A), the part containing (C), and the part containing (C) and (A) on the adherend surface of one substrate A step of forming two or more parts selected from the group to form a curable polyorganosiloxane composition before curing; and step 2A: laminating the other substrate to form a curable polyorganosiloxane composition. The manufacturing method of the adhesive body containing the two base materials including the process of bonding together base materials.   Step 1A includes Step 1A-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and ( The manufacturing method of Claim 9 which is a process of laminating | stacking two or more layers chosen from the group which consists of a layer containing A), and forming the laminated body of a curable polyorganosiloxane composition.   Step 1A includes Step 1A-2: Three layers including a layer containing (C), a layer containing (B) and (A), and a layer containing (C) in this order on the adherend surface of one substrate. The manufacturing method according to claim 9, wherein the step is a step of forming a laminate of the curable polyorganosiloxane composition by laminating.   Step 1A is Step 1A-3: a layer containing (B) and (A), a layer containing (C), and a layer containing (B) and (A) on the adherend surface of one substrate. The method according to claim 9, wherein the layers are laminated in this order to form a laminate of the curable polyorganosiloxane composition. (A) an alkenyl group-containing polyorganosiloxane containing two or more alkenyl groups in the molecule;
(B) a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule; and (C) a platinum-based catalyst,
The ratio of the number H _B of hydrogen atoms bonded to the silicon atom in (B) to the number Vi _A of alkenyl groups in (A) is 0.5 to 100,
(C) is 0.5 to 1000 ppm as a platinum-based metal atom,
A method for producing an adhesive body comprising two substrates using a curable polyorganosiloxane composition,
Step 1B: From the part containing (B), the part containing (B) and (A), the part containing (C), and the part containing (C) and (A) on the adherend surface of one substrate Forming two or more parts selected from the group consisting of:
Step 2B: a part containing (B), a part containing (B) and (A), a part containing (C), and a part containing (C) and (A) on the adherend surface of the other substrate A step of forming one or more portions selected from the group consisting of: and step 3B: obtained in step 1B and step 2B via two or more portions obtained in step 1B and one or more portions obtained in step 2B. Including the step of bonding substrates together, the composition of the portion obtained by combining the portion obtained in step 1B and the portion obtained in step 2B is a composition of a curable polyorganosiloxane composition, and includes two substrates Manufacturing method of adhesive body. Step 1B includes Step 1B-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and ( A step of forming a laminate by forming two or more layers selected from the group consisting of layers comprising A),
Step 2B includes Step 2B-1: a layer containing (B), a layer containing (B) and (A), a layer containing (C), and (C) and (A) is a step of forming a laminate by forming one or more layers selected from the group consisting of layers comprising:
The manufacturing method according to claim 13. Step 1B is Step 1B-2: a step of laminating a layer containing (C) on the adherend surface of one substrate and then laminating a layer containing (B) and (A) to obtain a laminate. And
Step 2B is Step 2B-2: a step of obtaining a laminate by laminating a layer containing (C) on the adherend surface of the other substrate.
The manufacturing method of Claim 13 or 14. Step 1B is Step 1B-3: a step of laminating a layer containing (B) and (A) on the adherend surface of one substrate and then laminating a layer containing (C) to obtain a laminate. And
Step 2B is Step 2B-3: a step of obtaining a laminate by laminating a layer containing (B) and (A) on the adherend surface of the other substrate.
The manufacturing method of Claim 13 or 14.   One substrate is a base having an image display unit of the image display device, the other substrate is a translucent protective unit of the image display device, and the adhesive is an image display device. Item 17. The production method according to any one of Items 9 to 16.